CN105601914B - A kind of preparation method of ion liquid functionalization graphene/conductive polyaniline nano-wire composite - Google Patents
A kind of preparation method of ion liquid functionalization graphene/conductive polyaniline nano-wire composite Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
It is as follows the step of the preparation method the invention discloses a kind of preparation method of ion liquid functionalization graphene/conductive polyaniline nano-wire composite：(1) graphite oxide is prepared using chemical oxidization method, graphene oxide suspension is obtained by graphite oxide is scattered by ultrasonication in organic solvent；(2) graphene that ion liquid functionalization is made in potassium hydroxide is proportionally added into gained graphene oxide suspension；(3) by ion liquid functionalization graphene ultrasonic disperse in deionized water, the stable graphene suspension in upper strata is obtained by centrifuging；(4) aniline is added into graphene suspension to be uniformly mixed；(5) inorganic acid is configured, adds ammonium persulfate thereto, the mixed solution is rapidly added into step (4) resulting solution ion liquid functionalization graphene/conductive polyaniline nano-wire composite is made.The inventive method is simple and easy, cost is cheap, yield is high, chemical uniformity is good；Obtained ion liquid functionalization graphene/conductive polyaniline nano-wire composite can be widely used in the fields such as ultracapacitor, sensor, electronic device, fuel cell, electro-catalysis.
Description
Technical field
The present invention relates to novel energy technical field of material, more particularly to a kind of ion liquid functionalization graphene/
The preparation method of conductive polyaniline nano-wire composite.
Background technology
Ultracapacitor is a kind of new electrochemical energy storage device between traditional capacitor and secondary cell, tool
There are higher power density and long circulation life, in Aero-Space, electronic equipment, mobile communication, communications and transportation, Military Application etc.
Field has a wide range of applications；Electrode material is the key factor for determining ultracapacitor chemical property, and research and development are new
The electrode material of grain husk is the important channel for improving performance of the supercapacitor.Polyaniline is as a kind of typical pi-conjugated conductive polymer
Sub- material, there is raw material cheap and easy to get, convieniently synthesized, environment and good, the higher electrical conductivity of chemical stability, super
Capacitor, sensor, catalyst, electrochromic material etc. have broad application prospects；Electrically conductive polyaniline is to pass through electricity
The redox reaction storage High Density Charge of Rapid reversible occurs in pole surface or body phase, there is the higher counterfeit electricity of faraday
Hold, but electron transfer kinetics poor-performing, cycle life are short；This redox being primarily due in polymer backbone is lived
Property position be not unusual stable in repeated multiple times oxidation-reduction process.Graphene is tightly packed into two by single layer of carbon atom
A kind of carbonaceous new material of honeycomb crystal lattice structure is tieed up, there is excellent chemical stability, big specific surface area and wider electricity
Chemical window.Although single-layer graphene has a limit specific surface area of super large, graphene in preparation process due to piece with
There is stronger Van der Waals force between piece, the reunion and accumulation of lamella easily occurs, reduces the specific capacitance of graphene, limits it
Application as electrode material for super capacitor；By the way that graphene film strata can be reduced to graphenic surface functional modification
Collection.Monodimension nanometer material such as nanotube, nano wire, nanofiber etc. are except the spy of the high-specific surface area with other nanostructureds
Point outside, also with high length-diameter ratio and excellent conductive capability, thus ultracapacitor electrode material research field have weight
The researching value wanted；By the graphene of functional modification with conductive polyaniline nano-wire is compound constructs graphene/electrically conductive polyaniline
Nanowire composite, the electrochemical stability of polyaniline can be not only improved, while composite can be obviously improved as super
The specific capacitance of level capacitor electrode material.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of ion liquid functionalization graphene/conductive polyaniline nano-wire
The preparation method of composite.
To reach above-mentioned purpose, technical scheme is as follows：
A kind of preparation method of ion liquid functionalization graphene/conductive polyaniline nano-wire composite, the preparation
The step of method, is as follows：
(1) graphite oxide is prepared using chemical oxidization method, graphite oxide is dispersed in by organic solvent by ultrasonication
Middle acquisition graphene oxide suspension, glyoxaline ion liquid is added into graphene oxide suspension, it is small to be stirred at room temperature 5
When, then stand 24 hours and pour out upper strata graphene oxide suspension；
(2) add potassium hydroxide into gained graphene oxide suspension, and stirred 10 hours at 90-95 DEG C, by from
Heart separation, absolute ethyl alcohol and deionized water are repeatedly washed, and are then carried out freeze-drying process, are finally obtained ion liquid functionalization
Graphene；
(3) by ion liquid functionalization graphene ultrasonic disperse in deionized water, it is steady by centrifuging acquisition upper strata
Fixed graphene suspension, mass concentration 0.09-3.1mg/mL；
(4) aniline is added into graphene suspension, molar concentration 0.05-0.5mol/L, is stirred at 0-5 DEG C
Uniformly；
(5) inorganic acid is configured, molar concentration 2mol/L, adds ammonium persulfate, molar concentration 0.013- thereto
0.125mol/L, the mixed solution is rapidly added into step (4) resulting solution, then stirred 12 hours at 0-5 DEG C, institute
Product through filtering, absolute ethyl alcohol and deionized water be repeatedly after washing, under 60 DEG C, vacuum environment drying process obtain within 8 hours
Ion liquid functionalization graphene, conductive polyaniline nano-wire composite.
Preferably, the organic solvent is any one in N, dinethylformamide, ethanol, ethylene glycol.
Preferably, the inorganic acid is any one in perchloric acid, hydrochloric acid, sulfuric acid.
Preferably, the glyoxaline ion liquid is 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- fourths
Base -3- methylimidazole hexafluorophosphoric acids ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyls -
Any one in 3- methyl imidazolium tetrafluoroborate ionic liquids.
Pass through above-mentioned technical proposal, the beneficial effects of the invention are as follows：
The present invention carries out functional modification by glyoxaline ion liquid to graphene, using chemical oxidization method in ionic liquid
Body function graphite alkene suspension situ polymerization aniline prepares graphene/conductive polyaniline nano-wire composite, in graphite
Alkene surface introduces conductive polyaniline nano-wire；Utilize the big specific surface area of graphene, excellent electric conductivity and chemical stability etc.
Advantage, the electrical properties and stability of nano composite material are lifted, nano composite material can not only be significantly improved as super electricity
The charge and discharge cycles stability and specific capacitance of container electrode material, internal resistance and the solution resistance of ultracapacitor can also be reduced.
The present invention synthesizes electrically conductive polyaniline using chemical oxidation situ aggregation method on ion liquid functionalization graphene and received
Rice noodles, preparation method is simple and easy, reaction temperature is low, the reaction time is short, energy consumption is low, chemical uniformity is good, is easy to largely prepare,
And easily it is generalized to other material systems.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the SEM photograph of ion liquid functionalization graphene/conductive polyaniline nano-wire composite of the present invention.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, enter below
One step illustrates the present invention.
Embodiment 1
The invention discloses a kind of preparation side of ion liquid functionalization graphene/conductive polyaniline nano-wire composite
Method is as follows the step of the preparation method：
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 9ml ion liquid functionalizations in 100ml deionized waters, by centrifuging
Obtain the stable graphene suspension in upper strata, mass concentration 0.09mg/mL；913 μ L benzene is added into graphene suspension
Amine (0.93g, molar concentration 0.1mol/L), is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
100ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.025mol/L in 2mol/L perchloric acid solution, then will
The mixed solution is quickly adding into graphene/aniline mixed system, is stirred 12 hours at 0-5 DEG C, then by reaction solution
Pour into large beaker, add deionized water 500mL thereto, after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol
It is cleaned multiple times with deionized water, 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 1 of composite, graphene and polyaniline:99；Fig. 1 is ESEM (SEM) photo of the composite prepared, from
It can be seen that a diameter of 80nm polyaniline nano-line is dispersed in graphenic surface in figure.
Embodiment 2
The invention discloses a kind of preparation side of ion liquid functionalization graphene/conductive polyaniline nano-wire composite
Method is as follows the step of the preparation method：
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) the graphene ultrasonic disperse of 9mg ion liquid functionalizations is obtained in 30ml deionized waters by centrifugation
Obtain the stable graphene suspension in upper strata, mass concentration 0.3mg/mL；913 μ L aniline is added into graphene suspension
(0.93g, molar concentration 0.33mol/L), it is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in 30ml
Molar concentration is that the molar concentration of ammonium persulfate solution is 0.083mol/L, then mixes this in 2mol/L perchloric acid solution
Close solution to be quickly adding into graphene/aniline mixed system, stir 12 hours at 0-5 DEG C, then pour into reaction solution
In large beaker, deionized water 500mL is added thereto, and after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol and goes
Ionized water is cleaned multiple times, and it is compound that 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 1 of material, graphene and polyaniline:99.
Embodiment 3
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 19mg ion liquid functionalizations in 50ml deionized waters, by centrifuging
Obtain the stable graphene suspension in upper strata, mass concentration 0.38mg/mL；913 μ L benzene is added into graphene suspension
Amine (0.93g, molar concentration 0.2mol/L), is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
50ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.05mol/L, then mixes this in 2mol/L hydrochloric acid solution
Close solution to be quickly adding into graphene/aniline mixed system, stir 12 hours at 0-5 DEG C, then pour into reaction solution
In large beaker, deionized water 500mL is added thereto, and after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol and goes
Ionized water is cleaned multiple times, and it is compound that 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 2 of material, graphene and polyaniline:98.
Embodiment 4
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 28mg ion liquid functionalizations in 30ml deionized waters, by centrifuging
Obtain the stable graphene suspension in upper strata, mass concentration 0.93mg/mL；1370 μ L benzene is added into graphene suspension
Amine (1.4g, molar concentration 0.5mol/L), is uniformly mixed at 0-5 DEG C；0.86g ammonium persulfate is dissolved in 30ml
Molar concentration is that the molar concentration of ammonium persulfate solution is 0.125mol/L, then mixes this in 2mol/L sulfuric acid solution
Solution is quickly adding into graphene/aniline mixed system, is stirred 12 hours at 0-5 DEG C, is then poured into reaction solution greatly
In beaker, thereto add deionized water 500mL, stand 5 hours after, products therefrom through vacuum filtration, absolute ethyl alcohol and go from
Sub- water is cleaned multiple times, and 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire composite wood in 8 hours
The mass ratio 2 of material, graphene and polyaniline:98.
Embodiment 5
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 49mg ion liquid functionalizations in 50ml deionized waters, by centrifuging
Obtain the stable graphene suspension in upper strata, mass concentration 0.98mg/mL；913 μ L benzene is added into graphene suspension
Amine (0.93g, molar concentration 0.2mol/L), is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
50ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.05mol/L, then mixes this in 2mol/L sulfuric acid solution
Close solution to be quickly adding into graphene/aniline mixed system, stir 12 hours at 0-5 DEG C, then pour into reaction solution
In large beaker, deionized water 500mL is added thereto, and after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol and goes
Ionized water is cleaned multiple times, and it is compound that 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 5 of material, graphene and polyaniline:95.
Embodiment 6
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 103mg ion liquid functionalizations in 50ml deionized waters, by centrifuging
Obtain the stable graphene suspension in upper strata, mass concentration 2.06mg/mL；913 μ L benzene is added into graphene suspension
Amine (0.93g, molar concentration 0.2mol/L), is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
50ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.05mol/L, then mixes this in 2mol/L hydrochloric acid solution
Close solution to be quickly adding into graphene/aniline mixed system, stir 12 hours at 0-5 DEG C, then pour into reaction solution
In large beaker, deionized water 500mL is added thereto, and after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol and goes
Ionized water is cleaned multiple times, and it is compound that 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 10 of material, graphene and polyaniline:90.
Embodiment 7
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 164mg ion liquid functionalizations in 100ml deionized waters, by centrifugation point
The graphene suspension stable from upper strata is obtained, mass concentration 1.64mg/mL；Add 913 μ L's into graphene suspension
Aniline (0.93g, molar concentration 0.1mol/L), is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
100ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.025mol/L in 2mol/L perchloric acid solution, then will
The mixed solution is quickly adding into graphene/aniline mixed system, is stirred 12 hours at 0-5 DEG C, then by reaction solution
Pour into large beaker, add deionized water 500mL thereto, after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol
It is cleaned multiple times with deionized water, 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 15 of composite, graphene and polyaniline:85.
Embodiment 8
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 232mg ion liquid functionalizations in 200ml deionized waters, by centrifugation point
The graphene suspension stable from upper strata is obtained, mass concentration 1.16mg/mL；Add 913 μ L's into graphene suspension
Aniline (0.93g, molar concentration 0.05mol/L), is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
200ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.013mol/L, then should in 2mol/L sulfuric acid solution
Mixed solution is quickly adding into graphene/aniline mixed system, is stirred 12 hours at 0-5 DEG C, is then fallen reaction solution
Enter in large beaker, thereto add deionized water 500mL, stand 5 hours after, products therefrom through vacuum filtration, absolute ethyl alcohol and
Deionized water is cleaned multiple times, and it is multiple that 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 20 of condensation material, graphene and polyaniline:80.
Embodiment 9
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 400mg ion liquid functionalizations in 200ml deionized waters, by centrifugation point
The graphene suspension stable from upper strata is obtained, mass concentration 2mg/mL；913 μ L aniline is added into graphene suspension
(0.93g, molar concentration 0.05mol/L), it is uniformly mixed at 0-5 DEG C；0.57g ammonium persulfate is dissolved in
200ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.013mol/L, then should in 2mol/L hydrochloric acid solution
Mixed solution is quickly adding into graphene/aniline mixed system, is stirred 12 hours at 0-5 DEG C, is then fallen reaction solution
Enter in large beaker, thereto add deionized water 500mL, stand 5 hours after, products therefrom through vacuum filtration, absolute ethyl alcohol and
Deionized water is cleaned multiple times, and it is multiple that 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 30 of condensation material, graphene and polyaniline:70.
Embodiment 10
(1) prepare graphite oxide using chemical oxidization method, by ultrasonication by 1g graphite oxides be dispersed in 500mlN,
In dinethylformamide (can also be ethanol or ethylene glycol), ultrasound 5 hours, the stable oxygen in upper strata be obtained by centrifuging
Graphite alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension
(glyoxaline ion liquid can be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazoles six
Fluorophosphate ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- ethyl-3-methylimidazole tetrafluoros
Any one in borate ion liquid), ionic liquid/graphene oxide mixture is stirred at room temperature 5 hours, then
Stand 24 hours and pour out upper strata graphene oxide suspension；2g potassium hydroxide is added into gained graphene oxide suspension, is surpassed
Sound 2 hours, and stirred 10 hours at 90-95 DEG C, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, Ran Houjin
Row freeze-drying process, finally obtain the graphene of ion liquid functionalization.
(2) by the graphene ultrasonic disperse of 310mg ion liquid functionalizations in 100ml deionized waters, by centrifugation point
The graphene suspension stable from upper strata is obtained, mass concentration 3.1mg/mL；457 μ L benzene is added into graphene suspension
Amine (0.465g, molar concentration 0.05mol/L), is uniformly mixed at 0-5 DEG C；0.29g ammonium persulfate is dissolved in
100ml molar concentrations are that the molar concentration of ammonium persulfate solution is 0.013mol/L in 2mol/L perchloric acid solution, then will
The mixed solution is quickly adding into graphene/aniline mixed system, is stirred 12 hours at 0-5 DEG C, then by reaction solution
Pour into large beaker, add deionized water 500mL thereto, after standing 5 hours, products therefrom is through vacuum filtration, absolute ethyl alcohol
It is cleaned multiple times with deionized water, 60 DEG C of vacuum drying obtain ion liquid functionalization graphene/conductive polyaniline nano-wire in 8 hours
The mass ratio 40 of composite, graphene and polyaniline；60.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (2)
- A kind of 1. preparation method of ion liquid functionalization graphene/conductive polyaniline nano-wire composite, it is characterised in that The step of preparation method, is as follows：（1）Graphite oxide is prepared using chemical oxidization method, 1g graphite oxides are dispersed in by 500mL N, N- by ultrasonication Graphene oxide suspension is obtained in dimethylformamide, ultrasound 5 hours, the stable oxidation stone in upper strata is obtained by centrifuging Black alkene suspension, mass concentration 2mg/mL；0.5g glyoxaline ion liquids are added into the graphene oxide suspension, will be from Sub- liquid/graphene oxide mixture is stirred at room temperature 5 hours, then stands 24 hours and pours out upper strata graphene oxide suspension Liquid；（2) 2g potassium hydroxide is added into gained graphene oxide suspension, it is ultrasonic 2 hours and small in 90-95 DEG C of stirring 10 When, repeatedly washed by centrifugation, absolute ethyl alcohol and deionized water, then carry out freeze-drying process, finally obtain ion The graphene of liquid functional；（3) the graphene ultrasonic disperse of 9ml ion liquid functionalizations is obtained in 100mL deionized waters by centrifugation The stable graphene suspension in upper strata is obtained, mass concentration is 0.09 mg/mL；（4) 913 μ L aniline is added into graphene suspension, molar concentration is 0.1 mol/L, is stirred at 0-5 DEG C Uniformly；（5) 0.57g ammonium persulfate is dissolved in the perchloric acid solution that 100mL molar concentrations are 2mol/L, ammonium persulfate The molar concentration of solution is 0.025mol/L, and then the mixed solution is quickly adding into graphene/aniline mixed system, Stir 12 hours at 0-5 DEG C, then pour into reaction solution in large beaker, add the mL of deionized water 500 thereto, it is small to stand 5 Shi Hou, products therefrom are cleaned multiple times through vacuum filtration, absolute ethyl alcohol and deionized water, and 60 DEG C of vacuum drying obtain ion in 8 hours Liquid functional graphite alkene/conductive polyaniline nano-wire composite.
- 2. a kind of ion liquid functionalization graphene/conductive polyaniline nano-wire composite according to claim 1 Preparation method, it is characterised in that the glyoxaline ion liquid be 1- butyl -3- methyl imidazolium tetrafluoroborates ionic liquid, 1- butyl -3- methylimidazole hexafluorophosphoric acids ionic liquid, 1- butyl -3- methylimidazole trifluoromethanesulfonic acids ionic liquid, 1- Any one in ethyl-3-methylimidazole tetrafluoroborate ion liquid.
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| CN108569689A (en) * | 2017-03-13 | 2018-09-25 | 杭州鼎牛投资管理有限公司 | A kind of preparation method for the graphene that purity is high, performance is stablized |
| CN106866961B (en) * | 2017-03-25 | 2018-07-27 | 山东宜建新材料技术有限公司 | A kind of preparation method of polyaniline composite ganoine conductive graphene material |
| CN106832921A (en) * | 2017-03-25 | 2017-06-13 | 山东本源晶体科技有限公司 | A kind of preparation method of ionic liquid doped polymer conductive graphene material |
| CN107603218A (en) * | 2017-10-18 | 2018-01-19 | 温州市赢创新材料技术有限公司 | A kind of graphene conductive material and preparation method thereof |
| CN109456478B (en) * | 2018-10-22 | 2021-04-02 | 东华大学 | Preparation method of graphene/polyaniline binary wave-absorbing material |
| CN110078919A (en) * | 2019-04-23 | 2019-08-02 | 桂林理工大学 | The method for preparing high-performance polymer using ionic liquid non-covalent modification graphene |
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| CN116814317A (en) * | 2023-05-26 | 2023-09-29 | 新乡市恒星科技有限责任公司 | Special lubricating grease for high-temperature-resistant conductive bearing and preparation method thereof |
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